CN106893124B - It is a kind of by polymer crystallization induce nanosphere ordered arrangement method and its in the application prepared on composite membrane - Google Patents

Abstract

The invention discloses a method for inducing orderly arrangement of nano-microspheres through polymer crystallization and its application in preparing a composite film. First, monodisperse PS-DVB nano-microspheres of different sizes were prepared by soap-free emulsion polymerization; the PS-DVB nano-microspheres prepared above were used as raw materials, PEG aqueous solutions of different concentrations were added, and the nano-microspheres were induced by crystallization of solution PEG. The spheres are arranged in order; and characterized by scanning electron microscopy and polarized light microscopy. The method is simple and easy to operate and has wide applicability. By further modifying the ordered microspheres, the composite material can be applied in different fields; and by replacing the crystalline polymer substrate that induces the ordered arrangement of the microspheres, the nanocomposite is expected to become a nanocomposite material with nano-microspheres. Modified and reinforced thin-film or bulk materials.

Description

A method for inducing ordered arrangement of nano-microspheres by polymer crystallization and its preparation Prepared for the application of composite membranes

technical field

The invention relates to the crystallization of organic polymer compounds and the field of nano-composite materials, in particular to a method for inducing ordered arrangement of nano-microspheres through polymer crystallization and its application in preparing composite films.

Background technique

Nanomaterials and nanocomposite materials are widely used in many fields such as optoelectronics, microelectronics, aerospace and aviation because of their unique structure and excellent performance. Nanospheres, as a typical structure of nanomaterials, have the advantages of controllable structure structure, and have many applications in optics and surface science. There are many methods for orderly arrangement of nano-microspheres, but they all have their own advantages and disadvantages. Scientists are constantly trying to find a method that is easy to operate and has wide practicability.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the deficiencies of the prior art, and provide a new way to induce the ordered arrangement of nano-microspheres, that is, a method for inducing the ordered arrangement of nano-microspheres through polymer crystallization and the method for preparing the composite membrane Applications.

One of the technical solutions adopted by the present invention to solve its technical problems is:

A method for inducing the orderly arrangement of nano-microspheres through polymer crystallization, firstly prepare PS-DVB nano-microspheres by a soap-free emulsion method, and then use solution PEG crystallization to induce the orderly arrangement of PS-DVB nano-microspheres; specifically including the following step:

1) Mix PS (styrene) and DVB (divinylbenzene), add deionized water, adjust the temperature to 75-85°C under the conditions of nitrogen protection, stirring, condensation and reflux, and then add the concentration dropwise to it. It is an initiator aqueous solution of 0.002-0.003g/ml, and the reaction is carried out for 8-10h; the volume ratio of the PS, DVB, and the initiator aqueous solution is 1-2:0.02-0.03:9-11;

2) After washing the product obtained by the reaction in step 1), PS-DVB (polystyrene-divinylbenzene) nano-microspheres are obtained, with a particle size of 400-500 nm; by controlling the amount of DVB, monodisperse PS of different sizes can be obtained -DVB nano-microspheres; it is formulated into PS-DVB nano-microsphere emulsion with a concentration of 8-12%;

3) The PS-DVB nano-microsphere emulsion with a concentration of 8-12% (mass volume percentage) obtained in step 2) is mixed with a 1-30% PEG aqueous solution in a volume ratio of 1:3-5 to obtain a mixed solution ; The PS-DVB nanospheres are induced to arrange orderly according to the growth direction of PEG crystals by crystallization of PEG in the mixed solution.

Specifically, in the step 3), the PEG crystallization in the mixed solution can be assisted by a drop film method, which includes: dropping the mixed solution on a flat pretreated glass substrate, and then placing the glass substrate on a 20- After drying at 40°C, the PS-DVB nanospheres were induced to arrange orderly according to the growth direction of PEG crystals through PEG crystallization, and a composite film formed by the orderly arrangement of PS-DVB nanospheres according to the growth direction of PEG crystals was obtained on the glass substrate.

Specifically, in the step 3), the PEG crystallization in the mixed solution can be assisted by a vertical deposition method, including: vertically inserting the pretreated glass substrate into the mixed solution, drying at 30-50° C. for 22-26 hours , the PS-DVB nanospheres are arranged in an orderly manner according to the growth direction of PEG crystals through PEG crystallization, and a composite film formed by the orderly arrangement of PS-DVB nanospheres according to the growth direction of PEG crystals is obtained on a glass substrate.

In a preferred experimental scheme of the present invention, the initiator is potassium persulfate (KPS).

In a preferred experimental scheme of the present invention, the PEG is a polymer with a molecular weight of 2000, namely PEG2000.

The second of the technical solutions adopted by the present invention to solve its technical problems is:

Application of the above method in preparing composite materials such as composite films.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The present invention provides a new way of inducing the orderly arrangement of nano-microspheres, that is, using polymer crystallization to induce the orderly arrangement of nano-microspheres according to the growth direction of dendrites, the method is simple to operate and has wide applicability; Further modification of the ordered nano-microspheres can apply the composite material to different fields; and the replacement of the crystalline polymer substrate that guides the ordered arrangement of the nano-microspheres makes the nanocomposite material promising to have nano-microspheres. Ball-modified and reinforced thin-film or bulk materials.

(2) The PS-DVB (polystyrene-divinylbenzene) nano-microspheres of the present invention are prepared by a soap-free emulsion polymerization method, the surfaces of the nano-microspheres are clean, and the post-processing is simple; the preparation method is simple, and the process is mature, low cost.

(3) The method for inducing the orderly arrangement of PS-DVB microspheres of the present invention is realized by solution state PEG crystallization, and has strong operability, simple device and good repeatability.

Description of drawings

The present invention will be further described below with reference to the accompanying drawings and embodiments.

1 is a scanning electron microscope image of PS-DVB (polystyrene-divinylbenzene) nano-microspheres obtained in Example 1 of the present invention.

2 is an optical microscope image (a) and a scanning electron microscope image (b) of the solution-state PEG crystal obtained in Example 1 of the present invention.

3 is a polarized light microscope image (a) and a scanning electron microscope image (b) of the ordered arrangement of PS-DVB microspheres induced by solution state PEG crystallization obtained in Example 1 of the present invention.

Detailed ways

Describe the content of the present invention in detail below by embodiment:

Example 1

1) Add 2mL PS and 0.03mL DVB to a 150mL three-necked flask, add 40mL deionized water, fix the device, pass in condensed water and nitrogen, then add a magnet for stirring, adjust the temperature to stabilize to 80°C, and use a syringe 10ml of aqueous solution containing 0.03g KPS was added dropwise to it, and the reaction was carried out for 8h;

2) The product obtained by the reaction in step 1) was washed twice with absolute ethanol, and then once with deionized water to obtain PS-DVB nano-microspheres with a particle size of 450 nm, which were made into 10% PS-DVB Nano-microsphere emulsion, placed in a 50mL centrifuge tube for later use;

3) Assist the PEG crystallization in the mixed solution by the drop film method or the vertical deposition method to induce the PS-DVB nano-microspheres to be arranged in an orderly manner according to the PEG crystal growth direction, specifically:

The orderly arrangement of PS-DVB nanospheres was induced by the drop film method to assist PEG crystallization: prepare 4 ml of PEG2000 aqueous solution with a concentration of 30%, and then add 1 ml of PS obtained in step 2) with a concentration of 10% and a particle size of 450 nm. -DVB nano-microsphere emulsion, after fully mixing, get a mixed solution; take a drop of mixed solution with a dropper, drop it on the pretreated (soaked in concentrated sulfuric acid, wash with deionized water and absolute ethanol respectively, cut it with a glass knife Appropriate size, soaked in absolute ethanol for use) on a glass substrate, and then put it into an oven at 30 ° C to dry to obtain a composite film after growth; The crystal growth directions are arranged in an orderly manner.

The orderly arrangement of PS-DVB nanospheres was induced by the vertical deposition method assisted by PEG crystallization: 4 ml of PEG2000 aqueous solution with a concentration of 30% was prepared, and then 1 ml of PS-DVB with a concentration of 10% and a particle size of 450 nm obtained in step 2) was prepared. The nano-microsphere emulsion was mixed with the PEG2000 aqueous solution to obtain a mixed solution, which was stored in a 50 mL centrifuge tube. The treated glass substrate (soaked in concentrated sulfuric acid for 24 hours, washed with deionized water and anhydrous ethanol, cut to a suitable size with a glass knife, soaked in anhydrous ethanol for later use) was blown dry with nitrogen, and inserted vertically into the glass substrate. The mixed solution was dried in an oven at 40 °C for 24 h to obtain a composite membrane after growth; on the composite membrane, the PS-DVB nano-microspheres were ordered according to the growth direction of PEG dendrites.

Example 2

1) Add 2mL PS and 0.03mL DVB to a 150mL three-necked flask, add 40mL deionized water, fix the device, pass in condensed water and nitrogen, then add a magnet for stirring, adjust the temperature to stabilize to 80°C, and use a syringe 10ml of aqueous solution containing 0.03g KPS was added dropwise to it, and the reaction was carried out for 10h;

2) The product obtained by the reaction in step 1) was washed twice with absolute ethanol, and then once with deionized water to obtain PS-DVB nano-microspheres with a particle size of 450 nm, which were made into 12% PS-DVB Nano-microsphere emulsion, placed in a 50mL centrifuge tube for later use;

3) Assist the PEG crystallization in the mixed solution by the drop film method or the vertical deposition method to induce the PS-DVB nano-microspheres to be arranged in an orderly manner according to the PEG crystal growth direction, specifically:

Using the drop film method to assist PEG crystallization to induce the orderly arrangement of PS-DVB nano-microspheres: prepare 4 ml of PEG2000 aqueous solution with a concentration of 20%, and then add 1 ml of PS obtained in step 2) with a concentration of 12% and a particle size of 450 nm. -DVB nano-microsphere emulsion, after fully mixing, get a mixed solution; take a drop of mixed solution with a dropper, drop it on the pretreated (soaked in concentrated sulfuric acid, wash with deionized water and absolute ethanol respectively, cut it with a glass knife Appropriate size, soaked in absolute ethanol for use) on a glass substrate, and then put it into an oven at 30 ° C to dry to obtain a composite film after growth; The crystal growth directions are arranged in an orderly manner.

The orderly arrangement of PS-DVB nanospheres was induced by the vertical deposition method assisted by PEG crystallization: 4 ml of PEG2000 aqueous solution with a concentration of 20% was prepared, and then 1 ml of PS-DVB with a concentration of 12% and a particle size of 450 nm obtained in step 2) was prepared. The nano-microsphere emulsion was mixed with the PEG2000 aqueous solution to obtain a mixed solution, which was stored in a 50 mL centrifuge tube. The treated glass substrate (soaked in concentrated sulfuric acid for 24 hours, washed with deionized water and anhydrous ethanol, cut to a suitable size with a glass knife, soaked in anhydrous ethanol for later use) was blown dry with nitrogen, and inserted vertically into the glass substrate. The mixed solution was dried in an oven at 40 °C for 24 h to obtain a composite membrane after growth; on the composite membrane, the PS-DVB nano-microspheres were ordered according to the growth direction of PEG dendrites.

Example 3

1) Add 2mL PS and 0.025mL DVB to a 150mL three-necked flask, add 40mL deionized water, fix the device, pass in condensed water and nitrogen, then add a magnet for stirring, adjust the temperature to stabilize to 80°C, and use a syringe 10ml of aqueous solution containing 0.03g KPS was added dropwise to it, and the reaction was carried out for 10h;

2) The product obtained by the reaction in step 1) was washed twice with absolute ethanol, and then once with deionized water to obtain PS-DVB nano-microspheres with a particle size of 420 nm, which were made into 10% PS-DVB Nano-microsphere emulsion, placed in a 50mL centrifuge tube for later use;

3) Assist the PEG crystallization in the mixed solution by the drop film method or the vertical deposition method to induce the PS-DVB nano-microspheres to be arranged in an orderly manner according to the PEG crystal growth direction, specifically:

Using the drop film method to assist PEG crystallization to induce the ordered arrangement of PS-DVB nano-microspheres: prepare 4 ml of PEG2000 aqueous solution with a concentration of 10%, and then add 1 ml of PS obtained in step 2) with a concentration of 10% and a particle size of 420 nm. -DVB nano-microsphere emulsion, after fully mixing, get a mixed solution; take a drop of mixed solution with a dropper, drop it on the pretreated (soaked in concentrated sulfuric acid, wash with deionized water and absolute ethanol respectively, cut it with a glass knife Appropriate size, soaked in absolute ethanol for use) on a glass substrate, and then put it into an oven at 30 ° C to dry to obtain a composite film after growth; The crystal growth directions are arranged in an orderly manner.

The orderly arrangement of PS-DVB nanospheres was induced by the vertical deposition method assisted by PEG crystallization: 4 ml of PEG2000 aqueous solution with a concentration of 10% was prepared, and then 1 ml of PS-DVB with a concentration of 10% and a particle size of 420 nm obtained in step 2) was prepared. The nano-microsphere emulsion was mixed with the PEG2000 aqueous solution to obtain a mixed solution, which was stored in a 50 mL centrifuge tube. The treated glass substrate (soaked in concentrated sulfuric acid for 24 hours, washed with deionized water and anhydrous ethanol, cut to a suitable size with a glass knife, soaked in anhydrous ethanol for later use) was blown dry with nitrogen, and inserted vertically into the glass substrate. The mixed solution was dried in an oven at 40 °C for 24 h to obtain a composite membrane after growth; on the composite membrane, the PS-DVB nano-microspheres were ordered according to the growth direction of PEG dendrites.

Example 4

1) Add 1mL PS and 0.02mL DVB to a 150mL three-necked flask, add 30mL deionized water, fix the device, pass in condensed water and nitrogen, then add a magnet for stirring, adjust the temperature to stabilize to 80°C, and use a syringe 10ml of aqueous solution containing 0.02g KPS was added dropwise to it, and the reaction was carried out for 8h;

2) The product obtained by the reaction in step 1) was washed twice with absolute ethanol, and then once with deionized water to obtain PS-DVB nano-microspheres with a particle size of 400 nm, which were made into 8% PS-DVB Nano-microsphere emulsion, placed in a 50mL centrifuge tube for later use;

3) Assist the PEG crystallization in the mixed solution by the drop film method or the vertical deposition method to induce the PS-DVB nano-microspheres to be arranged in an orderly manner according to the PEG crystal growth direction, specifically:

The orderly arrangement of PS-DVB nano-microspheres was induced by the drop film method to assist PEG crystallization: prepare 4 ml of PEG2000 aqueous solution with a concentration of 5%, and then add 1 ml of PS obtained in step 2) with a concentration of 8% and a particle size of 400 nm. -DVB nano-microsphere emulsion, after fully mixing, get a mixed solution; take a drop of mixed solution with a dropper, drop it on the pretreated (soaked in concentrated sulfuric acid, wash with deionized water and absolute ethanol respectively, cut it with a glass knife Appropriate size, soaked in absolute ethanol for use) on a glass substrate, and then put it into an oven at 30 ° C to dry to obtain a composite film after growth; The crystal growth directions are arranged in an orderly manner.

The orderly arrangement of PS-DVB nanospheres was induced by the vertical deposition method assisted by PEG crystallization: 4 ml of PEG2000 aqueous solution with a concentration of 5% was prepared, and then 1 ml of PS-DVB with a concentration of 8% and a particle size of 400 nm obtained in step 2) was prepared. The nano-microsphere emulsion was mixed with the PEG2000 aqueous solution to obtain a mixed solution, which was stored in a 50 mL centrifuge tube. The treated glass substrate (soaked in concentrated sulfuric acid for 24 hours, washed with deionized water and anhydrous ethanol, cut to a suitable size with a glass knife, soaked in anhydrous ethanol for later use) was blown dry with nitrogen, and inserted vertically into the glass substrate. The mixed solution was dried in an oven at 40 °C for 24 h to obtain a composite membrane after growth; on the composite membrane, the PS-DVB nano-microspheres were ordered according to the growth direction of PEG dendrites.

Example 5

1) Add 1mL PS and 0.02mL DVB to a 150mL three-necked flask, add 40mL deionized water, fix the device, pass in condensed water and nitrogen, then add a magnet for stirring, adjust the temperature to stabilize to 80°C, and use a syringe 10ml of aqueous solution containing 0.02g KPS was added dropwise to it, and the reaction was carried out for 8h;

2) The product obtained by the reaction in step 1) was washed twice with absolute ethanol, and then once with deionized water to obtain PS-DVB nano-microspheres with a particle size of 400 nm, which were made into 10% PS-DVB Nano-microsphere emulsion, placed in a 50mL centrifuge tube for later use;

3) Assist the PEG crystallization in the mixed solution by the drop film method or the vertical deposition method to induce the PS-DVB nano-microspheres to be arranged in an orderly manner according to the PEG crystal growth direction, specifically:

Using the drop film method to assist PEG crystallization to induce the ordered arrangement of PS-DVB nano-microspheres: prepare 4 ml of PEG2000 aqueous solution with a concentration of 1%, and then add 1 ml of PS obtained in step 2) with a concentration of 10% and a particle size of 400 nm. -DVB nano-microsphere emulsion, after fully mixing, get a mixed solution; take a drop of mixed solution with a dropper, drop it on the pretreated (soaked in concentrated sulfuric acid, wash with deionized water and absolute ethanol respectively, cut it with a glass knife Appropriate size, soaked in absolute ethanol for use) on a glass substrate, and then put it into an oven at 30 ° C to dry to obtain a composite film after growth; The crystal growth directions are arranged in an orderly manner.

The orderly arrangement of PS-DVB nanospheres was induced by the vertical deposition method assisted by PEG crystallization: 4 ml of PEG2000 aqueous solution with a concentration of 1% was prepared, and then 1 ml of PS-DVB with a concentration of 10% and a particle size of 400 nm obtained in step 2) was prepared. The nano-microsphere emulsion was mixed with the PEG2000 aqueous solution to obtain a mixed solution, which was stored in a 50 mL centrifuge tube. The treated glass substrate (soaked in concentrated sulfuric acid for 24 hours, washed with deionized water and anhydrous ethanol, cut to a suitable size with a glass knife, soaked in anhydrous ethanol for later use) was blown dry with nitrogen, and inserted vertically into the glass substrate. The mixed solution was dried in an oven at 40 °C for 24 h to obtain a composite membrane after growth; on the composite membrane, the PS-DVB nano-microspheres were ordered according to the growth direction of PEG dendrites.

The above descriptions are only preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly, that is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the description should still be covered by the present invention. within the range.

Claims (5)

1. a method for inducing ordered arrangement of nano-microspheres by polymer crystallization is characterized in that: comprising: 1) Mix PS and DVB, add deionized water, adjust the temperature to 75～85°C under the conditions of nitrogen protection, stirring, condensation and reflux, then dropwise add an initiator with a concentration of 0.002～0.003g/ml to it Aqueous solution, react for 8～10h; the volume ratio of PS, DVB and initiator aqueous solution is 1～2:0.02～0.03:9～11; 2) After washing the product obtained by the reaction in step 1), PS-DVB nano-microspheres are obtained, which are prepared into PS-DVB nano-microsphere emulsions with a concentration of 8-12%; 3) Mix the PS-DVB nano-microsphere emulsion with a concentration of 8-12% obtained in step 2) and the PEG aqueous solution of 1-30% according to the volume ratio of 1:3-5 to obtain a mixed solution; PEG crystallizes to induce PS-DVB nanospheres to be ordered according to the growth direction of PEG crystals; In the step 3), the PEG crystallization in the mixed solution is assisted by a drop film method, which includes: dropping the mixed solution on a flat pretreated glass substrate, and then drying the glass substrate at 20-40° C. , through PEG crystallization inducing the orderly arrangement of PS-DVB nanospheres according to the growth direction of PEG crystals, and obtaining a composite film formed by the orderly arrangement of PS-DVB nanospheres according to the growth direction of PEG crystals on a glass substrate; or, In the step 3), the PEG crystallization in the mixed solution is assisted by a vertical deposition method, including: vertically inserting the pretreated glass substrate into the mixed solution, drying at 30-50° C. for 22-26 hours, and crystallization through PEG. The PS-DVB nanospheres were induced to be arranged in an orderly manner according to the growth direction of PEG crystals, and a composite film formed by the orderly arrangement of PS-DVB nanospheres according to the growth direction of PEG crystals was obtained on a glass substrate. 2 . The method for inducing ordered arrangement of nano-microspheres by polymer crystallization according to claim 1 , wherein the initiator is potassium persulfate. 3 . 3 . The method for inducing ordered arrangement of nano-microspheres by polymer crystallization according to claim 1 , wherein the PEG is PEG2000. 4 . 4 . The method for inducing ordered arrangement of nano-microspheres by polymer crystallization according to claim 1 , wherein the particle size of the PS-DVB nano-microspheres is 400-500 nm. 5 . 5. A use of the method according to claim 1 in the preparation of a composite membrane.